Use of a secondary amine as a corrosion inhibiting and antimicrobial agent and an aqueous alkaline industrial fluid containing said amine

ABSTRACT

Secondary amines having the formula (I): R(Y) s  NHX, in which R is a hydrocarbon group having 2-12 carbon atoms, Y is the group --CH(OH)CH 2  --, --OCH 2  CH(OH)CH 2  -- or --O(CH 2 ) 3 , X is an alkyl group having 2-3 carbon atoms and substituted with hydroxyl groups in the 2-position or in the 2 - and 3-positions, and s is 0 or 1 with the condition that when s is 0, then X is an alkyl group substituted in the 2- and 3-positions, or a salt thereof, are used as anticorrosion and antimicrobial agents. They are suitable to be incorporated in aqueous, alkaline, industrial fluids. An aqueous, alkaline metal working fluid is also disclosed.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to the use of a secondary amine as acorrosion inhibiting and antimicrobial agent especially cially in anaqueous alkaline industrial fluid, such as an aqueous metal workingfluid. The effects of the secondary amine are especially favourable at apH value above 8.

2. Description of the Related Art

Water-based alkaline industrial fluids, such as metal working fluids,hydraulic fluids, coolants and cleaning fluids, undergo after some timeof use or storage undesirable changes which can be related to the factthat the components included in the fluids are degraded by bacteria,fungi and other micro-organisms. The microbial degradation considerablyreduces the life and the performance of the fluids. For example themicrobial degradation of the fluids may destroy the corrosion inhibitingand lubricating properties. From an economic point of view, it istherefore of great importance that microbial degradation of fluids ofthis type be minimised.

Well-known antimicrobial agents used in metal working fluids areformaldehyde or compounds giving off formaldehyde. Since formaldehydereadily evaporates from the fluid in open systems, the formaldehydecontent will be successively reduced and the surrounding aircontaminated with formaldehyde at the same time.

Other antimicrobial agents are quaternary ammonium compounds, but theiruse, e.g. in metal working fluids, has involved many practical problems,for instance because of reaction with organic acids and anionicsurfactants that may be present in the formulation.

The use, as antimicrobial agents, of reaction products of boric acid anda number of organic compounds, such as alkanolamines and carboxylicacids is also known in cutting fluids. However, such reaction productshave been found to have a relatively low antimicrobial effect, primarilyon fungi, and must therefore be used in relatively large amounts.

From articles by E. O. Bennett, e.g. his article in J. A. Soc. Lubr.Eng., 35 (1979), 137-144, U.S. Pat. No. 4,749,503, and European PatentApplication 412 089, it is known that secondary and tertiaryalkanolamine compounds substituted by hydrocarbon groups having 1-18carbon atoms have an antimicrobial effect in cutting fluids andcoolants.

The use of a number of alkoxylated amines and alkanolamines in order toobtain a tool life extension is known from European Patent ApplicationsNos. 196,810 and 192,358. For metal working fluids containingN-methylethanolamine a lowered susceptibility to the growth of mold andbacteria is reported. From the European Patent 180,561 it is also knownthat certain tertiary alkanolamines have corrosion inhibiting effects inmetal working fluids.

Alkanolamines, such as monoethanolamine, diethanolamine,diisopropanolamine and triethanolamine, have frequently been used ascorrosion inhibiting agents in aqueous alkaline industrial fluids. FromU.S. Pat. Nos. 3,280,029 and 4,976,919 and European Publication No180,561, it is well-known to use secondary and tertiary alkylalkanolamines as corrosion inhibiting agents.

SUMMARY OF THE INVENTION

According to the present invention it has now been found that secondaryamines having the formula

    R(Y).sub.s NHX                                             (I)

in which R is an hydrocarbon group having 2-12 carbon atoms, Y is thegroup --CH(OH)CH₂ --, --CH₂ CH(OH)CH₂ --, or --O(CH₂)₃ --, X is an alkylgroup having 2-3 carbon atoms and substituted with hydroxyl groups inthe 2-position or in the 2- and 3-positions, and s is 0 or 1 with thecondition that when s is 0, then X is an alkyl group substituted in the2- and 3-positions, or a salt thereof, have good corrosion inhibitingeffects as well as excellent antimicrobial effects and can be used inthe preparation of aqueous alkaline industrial fluids, such as metalworking fluids, hydraulic fluids, coolants, heat transfer media andcleaning fluids. These industrial fluids contain organic compounds forachieving specific technical effects. As the industrial fluids are oftenstored and/or used for a long time they are frequently subject toattacks by microorganisms whereby the amount of the organic compoundsare reduced as well as the desired effects e.g. anticorrosion effectsobtained by their presence. It is a well-known fact that especiallyaqueous metal working fluids are strongly exposed to bacteria and fungi.However, the secondary amines of formula I have proved to be veryeffective as anticorrosion and antimicrobial agents under the conditionspresent in aqueous synthetic and semi-synthetic metal working fluids.The fact that the secondary amines have antimicrobial efficacy alsodirectly supports the maintenance of corrosion inhibiting properties ofthe same amines. The aqueous alkaline fluid of the invention may be inthe form of an emulsion, microemulsion, colloidal solution or a truesolution.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Preferred embodiments of the secondary amines of formula I are thoseencompassed by the formulae

    RCH(OH)CH.sub.2 NHC.sub.2 H.sub.4 OH                       (II)

    RO(CH.sub.2).sub.3 NHC.sub.2 H.sub.4 OH                    (III)

    ROCH.sub.2 CH(OH)CH.sub.2 NHC.sub.2 H.sub.4 OH             (IV)

and

    RNHCH.sub.2 CH(OH)CH.sub.2 OH                              (V)

in which R has the meaning stated above, or a salt thereof.

Especially compounds having the R-groups not directly linked to thenitrogen atom, i.e. the compounds with formulae II, III and IV, or asalt thereof, have a good iron corrosion inhibiting effect.

The secondary amine compound of the formula I exhibit ex- cellentantimicrobial effects in synthetic formulations while in semisyntheticformulations those compounds having formula III usually are preferred.The amounts to be used of the secondary amines may vary within widelimits due to the speci- fic application area but it is normally from0.001-10% by weight, preferably from 0.01-2% by weight.

The secondary amines of the formula I may easily be prepared byconventional methods. For example secondary amine compounds of formulaII and IV may be prepared by reacting an olefin epoxide, preferably alinear alpha-olefin or the corresponding chloroglyceryl ether with anexcess of monoethanolamine at a temperature of 80°-120° C. and 60°-80°C. respectively. Secondary amines of formula III may be prepared byreacting an alcohol with acrylonitrile in the presence of alkali such asNaOH or KOH, or the corresponding alcolates. The obtained nitrilecompound is hydrogenated into a primary amine in the presence of aconventional hydrogenation catalyst and then ethoxylated to a secondaryamine of formula III. If desired the secondary amine containing reactionmixture is purified by fractional distillation. By reacting2,3-epoxy-1-propanol with an excess of a primary amine, secondary aminesof formula V are obtained in high yields with respect to the epoxycompound. If desired, the secondary amine may be used in form of a saltsoluble in water and/or oil. Especially preferred are salts withpharmaceutically acceptable anions. Specific examples of salts arephosphates, sulphates, phosphonates, sulphonates and carboxylates. Theacyclic hydrocarbon group R in the secondary amine of formula (I) may bestraight or branched, saturated or unsaturated. Preferably it is astraight hydrocarbon group with 4-10 carbon atoms. Most preferably R isa C₆₋₈ -alkyl group. Examples of suitable groups are butyl, hexyl, octyland decyl.

The metal working fluid according to the invention has preferably a pHvalue of at least 8, most preferably between 8 and 10, and contains asecondary amine having the formula I or a salt thereof in an amount of0.001 to 10% by weight, preferably 0.01 to 2% by weight.

In addition to the secondary amine the metal working fluid may containlubricants and other corrosion inhibitors.

The corrosion inhibitors are normally present in an amount of 0.1-10%,preferably 0.2-3%, by weight of the metal working fluid. Examples ofsuitable corrosion inhibitors are besides the secondary amines offormula I, other amine compounds, such as mono-, di- or triethanolamine,alkali metal hydroxides, triazole or thiadiazole compounds,monocarboxylic acids having 6-11 carbon atoms and dicarboxylic acids,preferably having 6-12 carbon atoms, such as azelaic acid or sebacicacid, alkyl- or aryl-sulphonamidocarboxylic acids; inorganic acids, suchas boric acid, and conventional reaction products between boric acidand/or carboxylic acids with organic compounds, such as alkanolamines.Examples of corrosion inhibitors are also the amine compounds describedin European Publication No. 180,561.

In order to increase the friction-reducing capacity, the metal workingfluids may also contain lubricants. They are usually selected from thegroup consisting of esters or amides of mono- or dicarboxylic acidshaving at least 10 carbon atoms in the acyl groups; monocarboxylic acidshaving 12 or more carbon atoms; dicarboxylic acid having more than 12carbon atoms; organic phosphate esters containing one or two hydrocarboncarbon groups having 6-18 carbon atoms; nonionic alkylene oxide adductshaving a molecular weight above 400, such as polypropylene glycol orrandomly distributed polypropylene ethylene glycols or block polymers ofethylene and propylene oxide and mixtures thereof; and oils. The amountof the lubricant is 0.05-10%, preferably 0.1-2%, by weight of the metalworking fluid. Preferably the monocarboxylic acid lubricants are coconutfatty acids, oleic acid, groundnut acids and rapeseed acids and estersand amides of these acids with polyols, such as glycerol,trimethylolpropane, pentaerythritol and polyalkylene glycols, andalkanolamines respectively. The hydrocarbon groups of the organicphosphate esters can be octyl, nonyl, decyl,dodecyl,tetradecyl andhexadecyl as well as their corresponding unsaturated alkenyl groups.Anionic lubricants also have a corrosion-preventing capacity againstiron.

The metal working compounds containing an oil as a lubricant have oftenthe form of an emulsion or a colloidal solution. With the term "oil" ishere understood a class of substances of synthetic, mineral, vegetableor animal origin. Usually, they are from petroleum or arepetroleum-derived but synthetic hydrocarbons such as poly-alpha-olefins(PAO's) or alkylates, such as alkyl benzenes, are also used. Thesecompositions also include emulsifying agents which are usually nonionicand/or anionic surfactants. Examples of anionic surfactants arealkylaryl sulphonates, such as dodecylbenzene sulphonates,alkylsulphates; such as sulphates of alcohols or alkoxylated alcohols;sulphated esters, such as sulphated castor oil; and phosphates ofalcohols or ethoxylated alcohols. Examples of nonionic surfactants arealkoxylated alkyl phenols, alcohols, carboxylic acids, alkanolamines,alkylamines and alkylamides. The alkoxylation agent is normally analkylene oxide containing 2-4 carbon atoms. Preferably at least 50% ofthe alkyleneoxy groups are ethyleneoxy groups and they may be eitherarranged in blocks or distributed at random. In a preferred embodimentthe polyoxyalkylene is end-capped with propyleneoxy and/or butyleneoxyunits in order to obtain a low-foaming surfactant. The anionic andnonionic surfactants are normally so chosen that they contain 8-20carbon atoms in a hydrocarbon residue. By the amount of ethyleneoxyunits in the surfactant the HLB-balance can be further regulated.

In addition to corrosion inhibitors and lubricants, the metal workingfluid may advantageously also contain pH-adjusting agents, metal complexstabilizers, defoamers, perfumes, viscosity-adjusting andsolubility-improving agents in known manner. Suitablesolubility-improving agents are glycols, such as hexylene glycol;alcohols, such as tridecanol and oleylalcohol; and glycol ethers, suchas butyldioxitol and butyltrioxitol.

Aqueous heat transfer media are for instance used in cooling towers,municipal hot water distribution systems and building heating systems,while coolants are used in metal working and quenching processes. Heattransfer media and coolants of the invention usually contains, inaddition to the secondary amine of formula I or a salt thereof,corrosion inhibitors, metal complexing agents, antiscaling agents,dispersing agents and/or pH-regulating agents. The hydraulic fluids mayalso contain lubricants and viscosity regulating agents.

The cleaning fluids contain beside the secondary amine with the formulaI or a salt thereof, a surfactant with micelle forming power. Thesurfactant is anionic, cationic, amphoteric or nonionic. Normally ananionic surfactant or a combination of a nonionic surfactant and ananionic surfactant is preferred. The cleaning fluids also compriseconventional additives, such as inorganic builders, defoamers, foamboosters, metal complexing agents, solubilizers and corrosioninhibitors.

The present invention is further illustrated by the following Examples.

EXAMPLE 1

A semi-synthetic metal working fluid concentrate having an concentrationof 5% by weight was prepared from the following components.

    ______________________________________                                        Components              % by weight                                           ______________________________________                                        Refined paraffinic oil  40.8-48.3                                             Sodium petroleum sulphonate (Mwt 440)                                                                 14.0                                                  Oleic acid              10.0                                                  Chlorinated paraffin (65% chlorine)                                                                   8.0                                                   50% aqueous potassium hydroxide                                                                       3.2                                                   Water                   2.0                                                   Neopentyl glycol dioleate                                                                             5.0                                                   Hexylene glycol          4.0-10.0                                             Tridecanol, branched    0.5-2.0                                               Amine in accordance with tables 1-4                                                                   5.0                                                   ______________________________________                                    

In order to obtain homogeneous compositions hexylene glycol andtridecanol may be incorporated in larger amounts than the minimum amountin the table above. The increased amounts added are balanced bycorresponding reductions in the amount of the refined paraffinic oil.

Anticorrosion performance was established using a modified version ofThe Institute of Petroleum IP 287/82 test method. In the modifiedprocedure deionised water was used instead of a synthetic water of 200ppm of calcium carbonate in the preparation of the test emulsion. Castiron chips were placed on Whatman number 6 filter paper and wetted withthe above formulation diluted with water for 2 hours at ambienttemperature. The percentage area stained was recorded.

The following tables show the anticorrosion performance where emulsionswere tested at pH 9.0 and 9.5. pH of the formulations was varied usingacetic acid/KOH.

                  TABLE 1                                                         ______________________________________                                        Corrosion tests using R--CH(OH)CH.sub.2 NHC.sub.2 H.sub.4 OH                                 Percent corrosion area for R                                   Dilution                                                                             pH    --     DIPA.sup.1)                                                                          C.sub.4 H.sub.9                                                                     C.sub.6 H.sub.13                                                                    C.sub.8 H.sub.17                                                                    C.sub.10 H.sub.21                ______________________________________                                        10:1   9.0   1      0      0     0     0     0                                15:1   9.0   2      5      0     0     0     0                                20:1   9.0   4      15     0     0     0     0                                30:1   9.0   17     65     1     1     1     1                                40:1   9.0   27     70     37    6     4     1                                10:1   9.5   0      0      0     0     0     0                                15:1   9.5   1      1      0     0     0     0                                20:1   9.5   4      2      0     0     0     0                                30:1   9.5   10     28     1     1     0     0                                40:1   9.5   35     45     2     1     1     0                                ______________________________________                                         .sup.1) Diisopropanolamine                                               

                  TABLE 2                                                         ______________________________________                                        Corrosion tests using R--O(CH.sub.2).sub.3 NHC.sub.2 H.sub.4 OH                              Percent corrosion area for R                                   Dilution                                                                             pH    --     DIPA.sup.1)                                                                          C.sub.4 H.sub.9                                                                     C.sub.6 H.sub.13                                                                    C.sub.8 H.sub.17                                                                    C.sub.10 H.sub.21                ______________________________________                                        10:1   9.0   1      0      0     0     0     0                                15:1   9.0   2      5      0     0     0     3                                20:1   9.0   4      15     0     0     0     3                                30:1   9.0   17     65     1     1     1     4                                40:1   9.0   27     70     19    1     1     7                                10:1   9.5   0      0      0     0     0     0                                15:1   9.5   1      1      0     0     0     0                                20:1   9.5   4      2      0     0     0     1                                30:1   9.5   10     28     1     0     0     2                                40:1   9.5   35     45     5     0     0     3                                ______________________________________                                         .sup.1) Diisopropanolamine                                               

                  TABLE 3                                                         ______________________________________                                        Corrosion tests using                                                         R--OCH.sub.2 CH(OH)CH.sub.2 --NH--CH.sub.2 CH.sub.2 OH                                       Percent corrosion area for R                                   Dilution                                                                             pH    --     DIPA.sup.1)                                                                          C.sub.4 H.sub.9                                                                     C.sub.6 H.sub.13                                                                    C.sub.8 H.sub.17                                                                    C.sub.10 H.sub.21                ______________________________________                                        10:1   9.0   1      0      1     0     0     0                                15:1   9.0   2      5      2     0     0     0                                20:1   9.0   4      15     4     1     0     0                                30:1   9.0   17     65     28    17    1     4                                40:1   9.0   27     70     35    38    2     14                               10:1   9.5   0      0      1     0     0     0                                15:1   9.5   1      1      2     0     0     0                                20:1   9.5   4      2      2     1     0     0                                30:1   9.5   10     28     5     4     0     1                                40:1   9.5   35     45     16    27    1     4                                ______________________________________                                         .sup.1) Diisopropanolamine                                               

                  TABLE 4                                                         ______________________________________                                        Corrosion tests using R--NH--CH.sub.2 CH(OH)CH.sub.2 OH                                      Percent corrosion area for R                                   Dilution                                                                             pH    --     DIPA.sup.1)                                                                          C.sub.4 H.sub.9                                                                     C.sub.6 H.sub.13                                                                    C.sub.8 H.sub.17                                                                    C.sub.10 H.sub.21                ______________________________________                                        10:1   9.0   1      0      0     1     0     0                                15:1   9.0   2      5      1     2     1     0                                20:1   9.0   4      15     2     3     1     1                                30:1   9.0   17     65     14    22    2     4                                40:1   9.0   27     70     63    30    9     5                                10:1   9.5   0      0      0     1     0     0                                15:1   9.5   1      1      1     2     0     0                                20:1   9.5   4      2      5     2     0     0                                30:1   9.5   10     28     9     11    2     1                                40:1   9.5   35     45     24    40    3     4                                ______________________________________                                         .sup.1) Diisopropanolamine                                                    From the results it is evident that all the secondary amines of the           invention have good corrosion inhibiting effects. Especially the secondar     amines having formulae II, III and IV exhibit excellent anticorrosion         properties.                                                              

EXAMPLE 2

Semi-synthetic and synthetic metalworking fluids were prepared from thefollowing base formulations with the amines disclosed in tables 5-12.

    ______________________________________                                        Semi-synthetic        Synthetic                                               concentrate           concentrate                                             formulation  %        formulation  %                                          ______________________________________                                        Refined paraffinic oil                                                                     14.2-38.2                                                                              Triethanolamine                                                                            47.4                                       Anionic surfactant                                                                         7.0      KOH (50%)     6.4                                       Naphthenic acid                                                                            5.5      Sebacic acid 16.5                                       Non-ionic surfactant                                                                       10.0     Water        9.7-25.7                                   Synthetic hydrocarbon                                                                      17.0     Amine        4.0-20.0                                   Tall oil amide                                                                             8.0                                                              Water        6.0                                                              KOH (50%)    2.3                                                              Tridecanol, branched                                                                        2.0-20.0                                                        Amine in accordance                                                                        4.0-20                                                           with table 5-12                                                               ______________________________________                                    

The amines were added in amounts of 4, 10 and 20% to provide 1000, 2500and 5000 ppm amine when diluted with water to a fluid concentration of2.5%. In order to obtain homogeneous compositions tridecanol may beadded in larger amounts than the minimum amounts in the table above. Theincreased amounts added are balanced by corresponding reductions in theamount of the mineral oil. The diluted fluids were subsequently testedwith respect to their bactericidal and fungicidal effects by addingstandardised bacterial and fungal inocula which were originally isolatedfrom contaminated metalworking fluids. The inocula used in the testswere prepared as described below.

Standardised Inoculum Preparation

(i) Bacteria

100 ml mineral salts media containing 2% trisodium citrate as solecarbon source (pH 9.0) in Erhlenmyer flasks were inoculated with 1 ml ofa culture of Pseudomonas aeruginosa at an optical cell density of 2.0measured at 650 nm (Perkin-Elmer UV-Vis Spectrophotometer, model Lambda2). These inocula were incubated at 30° C. in an orbital incubatorrotating at 200 rpm. During exponential growth (18 hour culture),further media were sub-inoculated in the same way, and the remainingculture harvested for testing of the diluted formulations. Thissubculturing procedure was continued until the end of the test period.

The cultures were harvested by centrifugation at 4000 rpm for 20 minutes(MSE Mistral 2000). The resulting bacterial pellet was resuspended insterile Hanks saline buffer solution and recentrifuged. Three suchwashes were performed. Prior to the final wash, the optical density wasadjusted to 2.0 (650 nm) and the volume of suspension noted. After thethird wash the bacterial cells were resuspended in Hanks saline bufferto one tenth of the original volume to provide a concentrated inoculumcontaining approximately 1×10¹⁰ cells ml⁻¹. This suspension was used asinoculum in the tests.

(ii) Fungi

100 ml mineral salts media containing 2% glucose as sole carbon sourcewere introduced into Erhlenmyer flasks and inoculated with 1 ml of ahomogenised culture of Cephalosporium sp. The inocula were incubated at30° C. in an orbital incubator rotating at 200 rpm. After 24 hours thefungus was homogenised and subcultured as already described into glucosesupplemented mineral salts media. The remaining culture was centrifugedat 4000 rpm for 20 minutes. After decanting the spent growth medium, thefungal pellet was resuspended in Hanks saline buffer and recentrifuged.After 3 washes, the final fungal pellet was resuspended in one tenth ofthe original volume of buffer used to provide a concentrated inoculum.This material was used as inoculum in the testing of the dilutedformulations.

Test method

2.5 ml of the formulations were diluted with 97.5 ml of sterile mineralsalts media introduced in 250 ml Erhlenmyer flasks. These dilutions wereadjusted to pH 9.5 by adding HCl or KOH. 200 microliters of thestandardised inocula were then added, either daily for the fullexperimental period providing a multiple inoculation, or singly, at thestart of the test with an inoculum consisting of a cell densityequivalent to the cumulative multiple inoculum. In this way, theinvestigation compared (i) the efficacy of the said amines followingrepeated additions where fresh supplementary biomass was introduced overa period to simulate a continuous contamination situation (i.e multipleinoculum test) and (ii) the efficacy of the said amines where a singlepresentation of biomass is performed and the long term effects on growthor survival can be monitored independently from the addition of freshbiomass (i.e single inoculation test). Total biomass levels in bothtests were comparable.

Both fluid types were inoculated separately with the bacterial andfungal biomass to avoid possible inhibitory interactions. Thesemi-synthetic fluids were tested over an experimental period of 28days, whereas satisfactory differentiation of amine performance could beachieved after 14 days in the synthetic fluids. All fluids wereincubated throughout the test at 30° C. in an orbital incubator rotatingat 200 rpm.

The survival of inocula, both in the multiple and single tests weremonitored daily. Fungi were monitored using conventional plate countingfollowing growth on malt extract agar (plus chloramphenicol) afterserial dilution. Bacteria were enumerated directly using the rapidautomated bacterial impedance technique (RABIT).

The following results were obtained.

                  TABLE 5                                                         ______________________________________                                        R--CH(OH)CH.sub.2 NHC.sub.2 H.sub.4 OH.                                       Efficacy against Cephalosporium.                                                                 Amine, ppm                                                                    0    1000   2500   5000                                    R      Inoculation                                                                             Formulation Mean log.sub.10 cfu/ml                           ______________________________________                                        C.sub.4 H.sub.9                                                                      single    semi-synth  3.72 1.47 1.40 0.83                              C.sub.6 H.sub.13                                                                     single    semi-synth  3.72 3.55 0.77 0.19                              C.sub.8 H.sub.17                                                                     single    semi-synth  3.72 2.02 0    0                                 C.sub.10 H.sub.21                                                                    single    semi-synth  4.09 0.59 0    0                                 C.sub.4 H.sub.9                                                                      multiple  semi-synth  4.37 4.05 3.25 3.19                              C.sub.6 H.sub.13                                                                     multiple  semi-synth  4.39 4.08 3.51 0.22                              C.sub.8 H.sub.17                                                                     multiple  semi-synth  4.39 3.79 1.94 0                                 C.sub.10 H.sub.21                                                                    multiple  semi-synth  4.09 3.11 2.61 0.50                              C.sub.4 H.sub.9                                                                      single    synthetic   3.46 0.94 0.72 0.69                              C.sub.6 H.sub.13                                                                     single    synthetic   3.46 0.93 0.43 0                                 C.sub.8 H.sub.17                                                                     single    synthetic   3.46 0    0    0                                 C.sub.10 H.sub.21                                                                    single    synthetic   3.96 0    0    0                                 C.sub.4 H.sub.9                                                                      multiple  synthetic   4.74 3.60 3.33 2.96                              C.sub.6 H.sub.13                                                                     multiple  synthetic   4.74 2.20 1.37 0                                 C.sub.8 H.sub.17                                                                     multiple  synthetic   4.74 0    0    0                                 C.sub.10 H.sub.21                                                                    multiple  synthetic   4.39 4.08 3.51 0.22                              ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                        R--O(CH.sub.2).sub.3 NHC.sub.2 H.sub.4 OH.                                    Efficacy against Cephalosporium.                                                                 Amine, ppm                                                                    0    1000   2500   5000                                    R      Inoculation                                                                             Formulation Mean log.sub.10 cfu/ml                           ______________________________________                                        C.sub.4 H.sub.9                                                                      single    semi-synth  3.72 3.51 0.80 0.40                              C.sub.6 H.sub.13                                                                     single    semi-synth  3.28 0.25 0.14 0                                 C.sub.8 H.sub.17                                                                     single    semi-synth  3.72 0.89 0.19 0                                 C.sub.10 H.sub.21                                                                    single    semi-synth  3.35 3.82 0.26 0                                 C.sub.4 H.sub.9                                                                      multiple  semi-synth  4.39 4.02 3.05 2.57                              C.sub.6 H.sub.13                                                                     multiple  semi-synth  3.85 3.86 2.84 0.12                              C.sub.8 H.sub.17                                                                     multiple  semi-synth  4.39 2.95 0    0                                 C.sub.10 H.sub.21                                                                    multiple  semi-synth  4.29 4.02 0.83 0                                 C.sub.4 H.sub.9                                                                      single    synthetic   3.46 0    0    0                                 C.sub.6 H.sub.13                                                                     single    synthetic   2.87 0    0    0                                 C.sub.8 H.sub.17                                                                     single    synthetic   3.46 0    0    0                                 C.sub.10 H.sub.21                                                                    single    synthetic   3.21 0    0    0                                 C.sub.4 H.sub.9                                                                      multiple  synthetic   4.74 3.16 2.07 1.72                              C.sub.6 H.sub.13                                                                     multiple  synthetic   3.87 0.30 0    0                                 C.sub.8 H.sub.17                                                                     multiple  synthetic   4.74 0    0    0                                 C.sub.10 H.sub.21                                                                    multiple  synthetic   4.67 0    0    0                                 ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                        R--OCH.sub.2 CH(OH)CH.sub.2 --NHC.sub.2 H.sub.4 OH.                           Efficacy against Cephalosporium.                                                                 Amine, ppm                                                                    0    1000   2500   5000                                    R      Inoculation                                                                             Formulation Mean log.sub.10 cfu/ml                           ______________________________________                                        C.sub.4 H.sub.9                                                                      single    semi-synth  3.72 3.23 2.46 3.38                              C.sub.6 H.sub.13                                                                     single    semi-synth  3.28 1.52 0.19 0.14                              C.sub.8 H.sub.17                                                                     single    semi-synth  3.72 2.41 0.79 0.11                              C.sub.10 H.sub.21                                                                    single    semi-synth  3.35 2.18 0.45 0                                 C.sub.4 H.sub.9                                                                      multiple  semi-synth  4.39 4.08 4.09 4.08                              C.sub.6 H.sub.13                                                                     multiple  semi-synth  3.85 4.01 3.77 2.92                              C.sub.8 H.sub.17                                                                     multiple  semi-synth  4.39 3.69 3.31 0.17                              C.sub.10 H.sub.21                                                                    multiple  semi-synth  4.29 4.33 3.82 1.78                              C.sub.4 H.sub.9                                                                      single    synthetic   3.45 0    0    0                                 C.sub.6 H.sub.13                                                                     single    synthetic   2.87 0    0    0                                 C.sub.8 H.sub.17                                                                     single    synthetic   3.46 0.24 0    0                                 C.sub.10 H.sub.21                                                                    single    synthetic   3.21 0    0    0                                 C.sub.4 H.sub.9                                                                      multiple  synthetic   3.96 0    0    0                                 C.sub.6 H.sub.13                                                                     multiple  synthetic   3.87 1.06 1.23 0.61                              C.sub.8 H.sub.17                                                                     multiple  synthetic   4.74 0    0    0                                 C.sub.10 H.sub.21                                                                    multiple  synthetic   4.67 0    0    0                                 ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                        R--NH--CH.sub.2 CH(OH)CH.sub.2 OH.                                            Efficacy against Cephalosporium.                                                                 Amine, ppm                                                                    0    1000   2500   5000                                    R      Inoculation                                                                             Formulation Mean log.sub.10 cfu/ml                           ______________________________________                                        C.sub.4 H.sub.9                                                                      single    semi-synth  3.28 1.48 1.16 0.52                              C.sub.6 H.sub.13                                                                     single    semi-synth  3.28 0.55 0.17 0                                 C.sub.8 H.sub.17                                                                     single    semi-synth  4.76 4.62 0.095                                                                              0                                 C.sub.10 H.sub.21                                                                    single    semi-synth  3.35 4.13 0.32 0.32                              C.sub.4 H.sub.9                                                                      multiple  semi-synth  3.85 4.38 4.31 4.14                              C.sub.6 H.sub.13                                                                     multiple  semi-synth  3.85 4.10 3.78 2.50                              C.sub.8 H.sub.17                                                                     multiple  semi-synth  5.02 4.62 0.40 0                                 C.sub.10 H.sub.21                                                                    multiple  semi-synth  4.29 4.06 1.84 0                                 C.sub.4 H.sub.9                                                                      single    synthetic   2.87 2.50 1.43 0                                 C.sub.6 H.sub.13                                                                     single    synthetic   2.87 0.43 0    0                                 C.sub.8 H.sub.17                                                                     single    synthetic   4.25 0    0    0                                 C.sub.10 H.sub.21                                                                    single    synthetic   3.21 0    0    0                                 C.sub.4 H.sub.9                                                                      multiple  synthetic   3.87 3.52 3.10 2.70                              C.sub.6 H.sub.13                                                                     multiple  synthetic   3.87 2.69 1.92 0.85                              C.sub.8 H.sub.17                                                                     multiple  synthetic   3.78 1.38 0.37 0                                 C.sub.10 H.sub.21                                                                    multiple  synthetic   4.67 0    0    0                                 ______________________________________                                    

                  TABLE 9                                                         ______________________________________                                        R--CH(OH)CH.sub.2 --NHCH.sub.2 CH.sub.2 OH.                                   Efficacy against Pseudomonas aeruginosa.                                                         Amine, ppm                                                                    0    1000   2500   5000                                    R      Inoculation                                                                             Formulation Mean log.sub.10 cfu/ml                           ______________________________________                                        C.sub.4 H.sub.9                                                                      single    semi-synth  9.43 8.41 0.56 0                                 C.sub.6 H.sub.13                                                                     single    semi-synth  9.43 7.38 0.85 0.18                              C.sub.8 H.sub.17                                                                     single    semi-synth  9.43 7.73 8.13 6.81                              C.sub.10 H.sub.21                                                                    single    semi-synth  8.22 8.24 6.14 6.04                              C.sub.4 H.sub.9                                                                      multiple  semi-synth  9.32 7.52 4.24 2.10                              C.sub.6 H.sub.13                                                                     multiple  semi-synth  9.32 6.88 4.69 0.82                              C.sub.8 H.sub.17                                                                     multiple  semi-synth  9.32 8.21 7.53 5.49                              C.sub.10 H.sub.21                                                                    multiple  semi-synth  8.70 8.10 7.21 7.19                              C.sub.4 H.sub.9                                                                      single    synthetic   8.25 6.32 0.75 0.73                              C.sub.6 H.sub.13                                                                     single    synthetic   8.25 6.42 0    0                                 C.sub.8 H.sub.17                                                                     single    synthetic   8.25 4.58 0    0                                 C.sub.10 H.sub.21                                                                    single    synthetic   8.59 7.71 3.79 7.10                              C.sub.4 H.sub.9                                                                      multiple  synthetic   7.73 5.99 4.03 3.75                              C.sub.6 H.sub.13                                                                     multiple  synthetic   7.73 5.65 0    0                                 C.sub.8 H.sub.17                                                                     multiple  synthetic   7.73 3.39 0    0                                 C.sub.10 H.sub.21                                                                    multiple  synthetic   7.94 7.38 7.14 5.60                              ______________________________________                                    

                  TABLE 10                                                        ______________________________________                                        R--O(CH.sub.2).sub.3 --NHCH.sub.2 CH.sub.2 OH.                                Efficacy against Pseudomonas aeruginosa.                                                         Amine, ppm                                                                    0    1000   2500   5000                                    R      Inoculation                                                                             Formulation Mean log.sub.10 cfu/ml                           ______________________________________                                        C.sub.4 H.sub.9                                                                      single    semi-synth  9.43 8.30 0.53 0                                 C.sub.6 H.sub.13                                                                     single    semi-synth  8.29 7.74 4.95 0                                 C.sub.8 H.sub.17                                                                     single    semi-synth  9.43 7.54 7.21 0                                 C.sub.10 H.sub.21                                                                    single    semi-synth  8.55 7.27 7.15 5.83                              C.sub.4 H.sub.9                                                                      multiple  semi-synth  9.32 7.55 4.63 0.92                              C.sub.6 H.sub.13                                                                     multiple  semi-synth  8.71 7.82 4.00 0                                 C.sub.8 H.sub.17                                                                     multiple  semi-synth  9.32 7.32 7.28 0                                 C.sub.10 H.sub.21                                                                    multiple  semi-synth  9.69 6.68 7.19 6.12                              C.sub.4 H.sub.9                                                                      single    synthetic   8.25 6.09 0.45 0                                 C.sub.6 H.sub.13                                                                     single    synthetic   8.63 0    0    0                                 C.sub.8 H.sub.17                                                                     single    synthetic   8.25 0    0    0                                 C.sub.10 H.sub.21                                                                    single    synthetic   6.98 0.80 0    0                                 C.sub.4 H.sub.9                                                                      multiple  synthetic   7.73 5.49 1.16 0                                 C.sub.6 H.sub.13                                                                     multiple  synthetic   8.46 2.46 0    0                                 C.sub.8 H.sub.17                                                                     multiple  synthetic   7.73 0    0    0                                 C.sub.10 H.sub.21                                                                    multiple  synthetic   7.53 3.18 0    0                                 ______________________________________                                    

                  TABLE 11                                                        ______________________________________                                        R--OCH.sub.2 CH(OH)CH.sub.2 --NHCH.sub.2 CH.sub.2 OH.                         Efficacy against Pseudomonas aeruginosa.                                                         Amine, ppm                                                                    0    1000   2500   5000                                    R      Inoculation                                                                             Formulation Mean log.sub.10 cfu/ml                           ______________________________________                                        C.sub.4 H.sub.9                                                                      single    semi-synth  9.43 8.47 8.08 7.57                              C.sub.6 H.sub.13                                                                     single    semi-synth  8.29 7.89 7.67 0                                 C.sub.8 H.sub.17                                                                     single    semi-synth  9.43 8.15 7.50 7.10                              C.sub.10 H.sub.21                                                                    single    semi-synth  8.55 8.07 8.96 7.78                              C.sub.4 H.sub.9                                                                      multiple  semi-synth  9.32 8.68 7.06 7.50                              C.sub.6 H.sub.13                                                                     multiple  semi-synth  8.71 8.23 6.90 3.48                              C.sub.8 H.sub.17                                                                     multiple  semi-synth  9.32 7.79 7.40 5.96                              C.sub.10 H.sub.21                                                                    multiple  semi-synth  9.69 6.94 8.39 7.21                              C.sub.4 H.sub.9                                                                      single    synthetic   8.59 6.76 0    0                                 C.sub.6 H.sub.13                                                                     single    synthetic   8.63 6.59 0    0                                 C.sub.8 H.sub.17                                                                     single    synthetic   8.25 6.01 5.74 1.48                              C.sub.10 H.sub.21                                                                    single    synthetic   6.98 6.18 5.74 5.71                              C.sub.4 H.sub.9                                                                      multiple  synthetic   7.94 4.87 3.55 0                                 C.sub.6 H.sub.13                                                                     multiple  synthetic   8.46 7.49 6.62 0                                 C.sub.8 H.sub.17                                                                     multiple  synthetic   7.73 6.39 4.09 0                                 C.sub.10 H.sub.21                                                                    multiple  synthetic   7.53 6.53 6.50 6.33                              ______________________________________                                    

                  TABLE 12                                                        ______________________________________                                        R--NHCH.sub.2 CH(OH)CH.sub.2 OH.                                              Efficacy against Pseudomonas aeruginosa.                                                         Amine, ppm                                                                    0    1000   2500   5000                                    R      Inoculation                                                                             Formulation Mean log.sub.10 cfu/ml                           ______________________________________                                        C.sub.4 H.sub.9                                                                      single    semi-synth  8.29 8.34 8.09 7.78                              C.sub.6 H.sub.13                                                                     single    semi-synth  8.29 7.99 7.24 0                                 C.sub.8 H.sub.17                                                                     single    semi-synth  9.16 6.75 4.18 2.80                              C.sub.10 H.sub.21                                                                    single    semi-synth  8.55 7.96 7.45 4.49                              C.sub.4 H.sub.9                                                                      multiple  semi-synth  8.71 8.30 6.83 7.85                              C.sub.6 H.sub.13                                                                     multiple  semi-synth  8.71 8.90 7.63 3.26                              C.sub.8 H.sub.17                                                                     multiple  semi-synth  8.42 6.91 6.82 1.27                              C.sub.10 H.sub.21                                                                    multiple  semi-synth  9.69 7.80 7.35 4.84                              C.sub.4 H.sub.9                                                                      single    synthetic   8.63 7.72 7.52 0.24                              C.sub.6 H.sub.13                                                                     single    synthetic   8.63 0    0    0                                 C.sub.8 H.sub.17                                                                     single    synthetic   7.74 2.49 0    0                                 C.sub.10 H.sub.21                                                                    single    synthetic   6.98 0    0    0                                 C.sub.4 H.sub.9                                                                      multiple  synthetic   8.46 8.06 7.47 7.55                              C.sub.6 H.sub.13                                                                     multiple  synthetic   8.46 8.15 2.96 0                                 C.sub.8 H.sub.17                                                                     multiple  synthetic   7.62 0    0    0                                 C.sub.10 H.sub.21                                                                    multiple  synthetic   7.53 0    0    0                                 ______________________________________                                    

It is evident that the secondary amines of the invention have excellentantimicrobial effects. Especially good results are shown by thealkanolamines of formula III in the semisynthetic formulations, whileall alkanolamines of the formulae II, III, IV and V exhibit excellentresults in the synthetic formulations.

What is claimed is:
 1. A process for providing a composition with acorrosion inhibiting and antimicrobial agent, comprising:incorporatinginto the composition an effective amount of a corrosion inhibiting andantimicrobial agent comprised of a secondary amine having a formula:

    R(Y).sub.s NHX                                             (I),

wherein:R is an hydrocarbon group having 2-12 carbon atoms, Y is a groupselected from the group consisting of --CH(OH)CH₂ --, --OCH₂ CH(OH)CH₂--, and --O(CH₂)₃ --, X is an alkyl group having 2-3 carbon atoms andbeing substituted by hydroxyl groups in one of the 2-position or the 2-and 3-positions, and s is 0 or 1 provided that when s is 0, then X isone of an alkyl group substituted in the 2- and 3-positions or a saltthereof.
 2. The process in accordance with claim 1, wherein R is analkyl group having 4-10 carbon atoms.
 3. The process in accordance withclaim 1, wherein the composition is an aqueous, alkaline industrialfluid.
 4. The process in accordance with claim 3, wherein the aqueous,alkaline industrial fluid is selected from the group consisting of ametal working fluid, a hydraulic fluid, a coolant, a heat transfermedium, and a cleaning fluid.
 5. The process in accordance with claim 1,wherein the secondary amine is present in the composition in an amountranging from 0.001 to 10% by weight.
 6. The process in accordance withclaim 5, wherein the secondary amine is present in the composition in anamount ranging from 0.01 to 2% by weight.
 7. The process in accordancewith claim 1, wherein the composition is a synthetic formulation,andwherein the corrosion inhibiting and antimicrobial agent is employedfor an antimicrobial effect.
 8. An aqueous alkaline metal working fluidwhich has a pH value of at least 8, comprising:from 0.001 to 10% byweight of a secondary amine having a formula:

    R(Y).sub.s NHX                                             (I),

wherein;R is an hydrocarbon group having 2-12 carbon atoms, Y is a groupselected from the group consisting of --CH(OH)CH₂ --, --OCH₂ CH(OH)CH₂--, and --O(CH₂)₃ --, X is an alkyl group having 2-3 carbon atoms andbeing substituted with hydroxyl groups in one of the 2-position or the2- and 3-positions, and s is 0 or 1 provided that when s is 0, then X isone of an alkyl group substituted in the 2- and 3-positions or a saltthereof.
 9. The aqueous alkaline metal working fluid in accordance withclaim 8, wherein the secondary amine is present in an amount rangingfrom 0.01 to 2% by weight.
 10. The aqueous alkaline metal working fluidin accordance with claim 8, wherein R is an alkyl group having 4-10carbon atoms.
 11. The aqueous alkaline metal working fluid in accordancewith claim 8, wherein the secondary amine has the formula RO(CH₂)₃ NHC₂H₄ OH.
 12. The aqueous alkaline metal working fluid in accordance withclaim 8, wherein the secondary amine has the formula RO(CH₂)₃ NHC₂ H₄OH, and wherein R is an alkyl group having 4-10 carbon atoms.
 13. Asolution containing the aqueous alkaline metal working fluid inaccordance with claim 18, wherein s in the formula of the secondaryamine is 1.